Pyrotechnic match capable of repeated ignition



Patented Sept. 18, 1951 PYROTECHNIC MATCH CAPABLE OF REPEATED IGNITION Folke Knut Knutsson-Hall, Lofta, .Sweden 'No Drawing. Application October 14, 1949, Serial No. 121,455. In Sweden November 13, 1946 Claims.

1 The present invention relates 'to a repeatedly ignitible match. More particularly the present invention relates to a match capable of generating in situ an igniting surface and capable of being extinguished and relita plurality of times. It has been previously proposed to provide various types of match which, in theory at least, were capable of being extinguished and again ignited by contact with a suitable friction surface. In general, however, the difficulty involved in preparing a match of this character was to provide a match which would light uponstriking and at the same time which would contain a s'ufficiently small amount of oxidizing agents and/or active constituents so that the same match could be easily extinguished. Although certain matches have been prepared which purported to solve this problem, up to the present time no such match has been successfully produced and utilized.

The present invention relates to a match of the general character above outlined, which operates upon an entirely new principle. In accordance with the present invention a coherent stick is prepared, which contains therein a proper proportioning of materials so that upon ignition of the stick at one of the ends thereof and after a suitable initial period of ignition and/or heating there is produced in situ a coating or deposit adjacent the flame, which contains the ignition materials in suitable concentration'to produce an initial spark and/or flame capable of igniting the remainder of the match end.

In other words, the match, according to the present invention, includes not only a combustion supporting agent which is capable of producing a substantially steady flame and of being volatilized, but a second combustion supporting agent in admixture with a suitable oxidizing agent, both of the latter two ingredients being substantially stable and non-combustible at the relatively low flame temperature of the first combustion supporting agent. In a match of this character, composed essentially of the aforementioned three ingredients, there is produced upon the ignition thereof and burning of the first combustion supporting agent an increasing concentration of the second two ingredients on the surface of the match adjacent the zone of combustion. The concentrated residue thus produced constitutes an ignition mass and upon striking the ignition mass against a phosphorus containing surface of the character ordinarily used for safety matches, a spark and initial flame is produced, which is sufficient to initiate proper ignition of the main or steady combustion supporting agent. 1

In generaL the ignition stick or match of the present invention is formed from a homogeneous plastic mass, including in initimate admixture a first combustion supporting agent capable of burning at a relatively low temperature such that the temperature of the flame atthe base thereof is below C. Such'combustion'supporting compounds are well 'known'in the prior art and include, for example, aldehydes such as metaldehyde, amines such "as hexamethylenetetramine and other amines, and also various alcohols such as methyl alcohol, ethyl alcohol, in admixture with higher alcohols suitable to lower the vapor *pressurethereof and preferably bodied with a suitable 'bodying agent so that a solid mass is produced. Preferably the primary combustion agent is solid at ordinary temperatures and is capable of burning substantially completely without leaving undesirable residues. A secondary combustion agent, which is capable of remaining on the surface after the combustion of the first agent, is a' compound capable of rapid ignitionin contact with achlorate or perchlorate oxidizing agent'when frictionally contacted with a phosphorus-containing surface. The secondary combustion agent should also be incapable of combustion or interaction with the chlorate or perchlorate oxidizing agent at any temperature corresponding to .the temperature at the base of the flame by the primary combustion agent. Preferably the combustion temperature of the secondary agent in admixture with the chlorate and perchlorate should be approximately 50 higher than the maximum temperature so that the minimum temperature of combustion or combination with chlorate should be above approximately C. Such a secondary combustion agent is preferably phthalic acid and/or derivatives thereof. The derivative of phthalic acid, which has been found to be especially suitable to the present purpose, is phenolphthalein. Other examples of suitable materials for the purpose are acetanilide and adipic acid, either alone or in combination with one another or in-combination with salicylic acid and/or 'benzoic acid.

In addition to the two combustion agents previously described, the material of the present invention also includes a suitable oxidizing agent such as chlorate or perchlorate salts. Preferably these are metal salts, such as the chlorates and perchlorates of sodium, potassium, ammonium and silver, but organic salts are also suitable.

With the three types of material just described there is also incorporated a binder such as resin, natural or synthetic, or a cellulose ester dissolved in a suitable solvent. If any substantial amount of binder is used, it is preferred that the binder be oxidizable or capable of combustion and prefably a cellulose ester, such as cellulose acetate or cellulose nitrate is especially suitable. However, other binders may be used and in some instances, where the match is molded under a relatively large amount of pressure, no binder is necessary.

The match of the present invention may be formed from the various ingredients hereinbefore set forth so as to be homogeneous throughout. On the other hand, for most purposes, it is desirable to form the stick by first preparing a core which will be richer in the secondary combustion agent and the chlorate or perchlorate oxidizing agent, and to cover this core with successive layers of material, each of the layers being successively richer in the primary combustion agent and having 'a lesser proportion of the chlorate or perchlorate and the secondary combustion agent. The purpose of so forming the stick is to produce the greatest amount of concentrate aftei each flame toward the center of the stick so that the stick will be easier to ignite by striking against a suitable surface. Thus, in practice, sticks have been formed wherein the concentration of the secondary combustion agent phenolpthalein and the chlorate or perchlorate oxidizing agent represented approximately 50% of the total composition at the center line of the match and descended in a substantially uniform manner to the outermost periphery of the match so that there was present at the periphery substantially no phenolpthalein and chlorate. Contrary to the disclosures of the prior art, the chlorate or perchlorate need not form a large part of the match, according to the present invention. Matches containing as low as of phenolpthalein and chlorate or perchlorate have been found entirely suitable. Even lesser quantities of oxidizing agents and phenolpthalein, or other secondary combustion agents, have been utilized, the only difference found being that the flame took a longer time to produce a concentrate at the surface adjacent the base thereof. In other words, if the match of the present invention contains a large proportion of the oxidizing agent and the secondary combustion agent a shorter period will be required to produce a surface concentrate or renewed ignition mass, and if a smaller proportion of the oxidizing agent and the secondary icombustion agent is used a longer period will be required. Matches may be made according to the present invention, which contain as high as 70% of chlorate or perchlorate together with the secondary combustion agent, such as phenolpthalein.

Preferably the phenolpthalein or other secondary imum, be present in the proportion of one part of phenolphthalein and two parts of the chlorate or perchlorate.

The outside of the rod or match is preferably given a coat of a suitable coating material. Vinyl alcohol derivatives, polyvinyl acetate, polyvinyl chloride, or copolymers of vinyl acetate and vinyl chloride are especially suitable as a coating material. Preferably when the coating is administered, the polyvinyls are utilized in a water emulsion and it is desirable, in a case where binders are used, to also utilize the various binders in water emulsion or suspension, since this minimizes the risk in manufacture as compared to the use of an inflammable solvent. The solid polyvinyl coating on the outside of the rod prevents the spread of flame along the outside and renders the same more suitable for use. This coating of the rod or match forms the subject matter of applicants copending application Serial No. 25,516, filed May 16, 1948.

While the phthalic acid and derivatives thereof has a main function as the secondary combustion agent, it has also been found that the presence of phthalic acid or its anhydrides or derivatives facilitates the proper combustion where metaldehyde or other polymeric aldehydes are utilized as the primary combustion agent, since it prevents the formation of smoke or dust from the sublimation of the polymeric aldehyde. This is believed due to the reaction of a portion of the phthalic anhydride to produce in situ from the metaldehyde ordinary ethyl alcohol, and upon burning a match of the present invention one can detect the odor of ethyl alcohol rather than the production of the large volume of white vapor characteristic of ordinary metaldehyde combustion.

The match of the present invention will not ignite when first prepared when struck against any surface, since no igniting mass or concentrate is then present. Preferably the rod or match of the present invention is burned or ignited by other means for the first ignition, and after being so ignited it may then be lit repeatedly by frictional contact with a suitable phosphorus-containing safety match striking surface. This type of surface, which is well known, usually contains, in addition to amorphous phosphorus, antimony sulfide together with a suitable abrasive, such as ground glass or pumice, the active ingredients being retained in position on a surface by a suitable binder, such as gum arabic. After the match of the present invention has been ignited and allowed to burn for a few seconds and then extinguished, a black concentrate or deposit will be noted at the previously ignited end. When the match is then struck against the safety match surface, a spark and an initial ignition is produced followed by the ignition of the main mass and the end of the rod will then burn until extinguished. During this burning a black formation is again observed at the end as soon as the ignition mass is reconstituted. If the black mass is removed from the end of the rod, the rod cannot be ignited, and if the black mass thus produced is analyzed, it is found to consist substantially entirely of a mixture of the secondary combustion agent, such as phenolphthalein and the oxidizing agent, i. e. chlorate or perchlorate.

In preparing the rod of the present invention, the various solid ingredients and the binder are carefully mixed together or kneaded and then allowed to dry for a sufiicient length of time to evaporate a proportion of the binder so as to produce a rather stifliy plastic mass. This mass may then be molded into a stick in any suitable manner. By proper proportioning of the binder solvents and solid ingredients, the mass may also be extruded in continuous production into sticks of any length. As previously pointed out, the stick may be made of a core together with successive layers. This may be done manually or the stick may be subjected to a successive extrusion process and/or extruded from a composite nozzle so that the outer layer or layers are formed about an inner core. After the stick is formed and dried, it may then be given an outer coating of a synthetic resin. The stick is then initially ignited and extinguished and is then ready for use. In the alternative, the stick may be provided with a match head, such as that utilized in an ordinary match, and such a match head will take the place of the initial roasting or ignition of the stick by'other means.

The following specific examples serve to illustrate but are not intended to limit the present invention:

Example I A basic mass consisting of 60 kgs. of solid alcohols or aldehydes is mixed with a solution of 10 kgs. of cellulose acetate in 50 kgs. of acetic ether or alcohol, said solution serving. as a binding agent for the basic mass. Then-the whole is worked well together in a kneading machine. Thereafter 20 kgs. of finely powdered sodium chlorate are added and incorporated with the mass already present. To this there is added kgs. of phthalic, acid and 5 kgs. of phenolphthalein serving as an agent having the combined effect to promote the ignition and cause enrichment. The whole is worked in the kneading machine to a plastic mass. In order to obtain a suitably hard mass, the kneading mass is subjected to vacuum, solvent thus evaporating, until the mass becomes appropriately hard for pressing into rods of a rather solid consistency. This is performed in a pressing machine, and the rods are cut into desirable lengths and allowed to dry. In order that the flame will not spread along the sides of the rods, their surfaces may be coated with, for instance, the basic mass described above having a high percentage of the binding agent described above incorporated therein. The surface thereafter may furthermore be provided with a coating, difficult to ignite, for instance of polyvinyl acetate, in order to improve the appearance, protect against moisture and further prevent the flame spreading along the surface of the rod.

Example II A solution of cellulose acetate was prepared by adding 100 gs. of cellulose acetate to 566 gs. of a mixed solvent consisting of 40% of acetone, 30% of ethylene dichloride, of ethyl alcohol, 18% of methanol and 2% of cyclohexanol.

gs. of the cellulose acetate solution were then stirred together in a porcelain mortar'with 2 gs. of phthalic acid anhydride and 3 /2 gs. of phenolphthalein. Thereafter, '7 gs. of finely powdered sodium chlorate and 2 gs. of metaldehyde were added and stirred lnto the mixture. The resultant paste was kneaded manually in front of a fan until the mass had assumed a rather stiff plastic consistency. The mass was then rolled to form rods of about 6 mm. in diameter. A rod of the type thus prepared was rubbed on a friction surface containing phosphorus withoutany result. However, after a rod of this type was initially ignited and allowed to burn for a sufiicient length of time to produce a substantial deposit on the end thereof it was easily ignitable on a friction surface and after being extinguished could be again ignited rapidly. A friction surface suitable for igniting the rod was prepared by forming a mixture of 10 gs. of antimony glance, 3 gs. of pumice, 0.10 gs. of potassium dichromate and 0.10 gs. of chalk. This mixture was stirred in a porcelain mortar to a proper consistency by the addition of 10 cc. of water. Thereafter 6.0 gs. of red phosphorus, 2.45 gs. of a 25% gum arabic solution and 0.42 gs. of a 25% bone glue solution were also mixed therewith. The mixture thus prepared was applied to ordinary cardboard by successively coating the same with the mixture by means of a brush, the final brushings utilizing a waterthinned mixture. After drying, the friction surface was suitable for igniting the rod previously described.

Ercample [III A second rod was prepared in a similar manner to that described in connection with Example II, except that the following proportions were used: 15.05 gs. of cellulose acetate solution, 1.5 gs. of phthalic acid anhydride, 3.00 gs. of phenolphthalein, 10 gs. of sodium chlorate and 9 gs. of metaldehyde. These rods, when properly prepared, function in a similar manner to the rods of Example II.

Example IV Rods were prepared by manually winding the soft rod of Example II helically about the core rod of Example III and the crude rod thus prepared was then rolled to form a smooth rod. The final rod, after drying, of this example, therefore, contained a higher proportion of sodium chlorate at the center thereof and after the ignition of the rod of this example the black mass produced at the surface was substantially higher at the center of the rod than the rods of Examples IIand III. This rod, therefore, proved easier to strike upon a friction surface.

The present application is a continuation-inpart of United States Patent Application Serial No. 782,215, filed October 25, 1947, now abandoned.

It will be obvious to those skilled in the art that various changes may be made without departingfrom the spirit of the invention and therefore the invention is not limited to what is described in the specification but only as indicated in the appended claims.

I claim:

1. A repeatably igniting match comprising a coherent stick including in homogeneous admixture a first vaporizable combustion supporting agent capable of burning substantially completely without leaving undesirable residues, having a relatively low temperature of combustion, and a low flame base temperature and selected from the group consisting of aldehydes, amines and alcohols and mixtures of aldehydes, amines and alcohols, an oxygen supplying salt having a decomposition temperature substantially higher than the flame base temperature of said first combustion supporting agent and selected from the group consisting of chlorates and perchlorates, and a second substantially non-volatile combustion supporting agent having a temperature of combustion, in the presence of the oxygen supplying salt, substantially higher than the flame base temperature of said first combustion supporting agent, said second combustion supporting agent being selected from the group con sisting of phthalic acid, derivatives of phthalic acid, acetanilide, adipic acid, mixtures of acetanilide and adipic acid, mixtures of acetanilide and salicylic acid, mixtures of acetanilide and benzoic acid, mixtures of adipic acid, acetanilide and salicylic acid and mixtures of acetanilide, adipic acid, salicylic acid and benzoic acid, so that upon combustion of said first combustion supporting agent a concentrate consisting substantially entirely of said oxygen supplying salt and said second combustion supporting agent is formed on the surface of saidstick adjacent the site of combustion, said concentrate being ignitable upon frictional contact with a phosphorus containing striking surface, said oxygen supplying salt together with said second combustion supporting agent not exceeding 70% by weight of the match.

2. The match of claim 1, wherein the second combustion supporting agent is phenolphthalein.

3. The match of claim 1, wherein the first combustion supporting agent is metaldehyde and the second combustion supporting agent is phenolphthalein.

4. A repeatably igniting match comprising a coherent stick including in homogeneous admixture, a first vaporizable combustion supporting agent capable of burning substantially completely without leaving undesirable residues, having a relatively low temperature of combustion and a flame base temperature below approximately 100 C. and selected from the group consisting of aldehydes, amines and alcohols and mixtures of aldehydes, amines and alcohols, an oxygen supplying salt having a decomposition temperature above approximately 150 C. and selected from the group consisting of chlorates and perchlorates, and a second substantially nonvolatile combustion supporting agent having a temperature of combustion in the presence of the oxygen supplying salt higher than approximately 150 C., said second combustion supporting agent being selected from the group consisting of phthalic acid, derivatives of phthalic acid, acetanilide, adipic acid, mixtures of acetanilide and adipic acid, mixtures of acetanilide and salicylic acid, mixtures of acetanilide and benzoic acid, mixtures of adipic acid, acetanilide and salicylic acid and mixtures of acetanilide, adipic acid, salicylic acid and benzoic acid, so that upon combustion of said first combustion supporting agent a concentrate consisting substantially entirely of said oxygen supplying salt and said second combustion supporting agent is formed on the surface of said stick adjacent the site of combustion, said concentrate being ignitible upon frictional contact with a phosphorus containing striking surface, said oxygen supplying salt together with said second combustion supporting agent not exceeding 70% by weight of the match.

5. A repeatably igniting match comprising a coherent stick provided with a surface coating for retarding the combustion of the surface thereof and including in homogeneous admixture a binder, a first vaporizable combustion supporting agent capable of burning substantially completely without leaving undesirable residues, having a relatively low temperature and selected from the group consisting of aldehydes, amines and alcohols and mixtures of aldehydes, amines and alcohols of combustion and a low flame base temperature, an oxygen supplying salt having a decomposition temperature substantially higher than the flame base temperature of said first combustion supporting agent and selected from the group consisting of chlorates and perchlorates, and a second substantially non-volatile combustion supporting agent having a temperature of combustion, in the presence of the oxygen supplying salt, substantially higher than the flame base temperature of said first combustion supporting agent, said second combustion supporting agent being selected from the group consisting of phthalic acid, derivatives of phthalic acid, acetanilide, adipic acid, mixtures of acetanilide and adipic acid, mixtures of acetanilide and salicylic acid, mixtures of acetanilide and benzoic acid, mixtures of adipic acid, acetanilide and salicylic acid and mixtures of acetanilide, adipic acid, salicylic acid and benzoic acid, so that upon combustion of said first combustion supporting agent a concentrate consisting substantially entirely of said oxygen supplying salt and said second combustion supporting agent is formed on the surface of said stick adjacent the site of combustion, said concentrate being ignitible upon frictional contact with a phosphorus containing striking surface, said oxygen supplying salt together with said second combustion supporting agent not exceeding by weight of the match.

6. The match of claim 1 wherein the second combustion supporting agent is adipic acid.

7. The match of claim 1 wherein the second combustion supporting agent is acetanilide.

8. The match of claim 1, wherein the second combustion supporting agent is a combination of phthalic acid and phenolphthalein.

9. The match of claim 1, wherein the first combustion supporting agent is metaldehyde and the second combustion supporting agent is a combination of phthalic acid and phenolphthalein.

10. The match of claim 1, wherein an outer layer is provided surrounding the said coherent stick that is richer in said first vaporizable combustion supporting agent, and having a lesser proportion of the oxygen supplying salt and the second combustion supporting agent.

FOLKE KNUT KNUTSSON-HALL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,004,436 Jaeger June 11, 1935 2,015,383 Konig et a1 Sept. 24, 1935 2,496,815 Ringer Feb. 7, 1950 FOREIGN PATENTS Number Country Date 500,219 Great Britain Feb. 6, 1939 

1. A REPEATABLY IGNITING MATCH COMPRISING A COHERENT STICK INCLUDING IN HOMOGENEOUS ADMIXTURE A FIRST VAPORIZABLE COMBUSTION SUPPORTING AGENT CAPABLE OF BURNING SUBSTANTIALLY COMPLETELY WITHOUT LEAVING UNDESIRABLE RESIDUES, HAVING A RELATIVELY LOW TEMPERATURE OF COMBUSTION, AND A LOW FLAME BASE TEMPERATURE AND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES, AMINES AND ALCOHOLS AND MIXTURES OF ALDEHYDES, AMINES AND ALCOHOLS, AN OXYGEN SUPPLYING SALT HAVING A DECOMPOSITION TEMPERATURE SUBSTANTIALLY HIGHER THAN THE FLAME BASE TEMPERATURE OF SAID FIRST COMBUSTION SUPPORTING AGENT AND SELECTED FROM THE GROUP CONSISTING OF CHLORATES AND PERCHLORATES, AND A SECOND SUBSTANTIALLY NON-VOLATILE COMBUSTION SUPPORTING AGENT HAVING A TEMPERATURE OF COMBUSTION, IN THE PRESENCE OF THE OXYGEN SUPPLYING SALT, SUBSTANTIALLY HIGHER THAN THE FLAME BASE TEMPERATURE OF SAID FIRST COMBUSTION SUPPORTING AGENT, SAID SECOND COMBUSTION SUPPORTING AGENT BEING SELECTED FROM THE GROUP CONSISTING OF PHTHALIC ACID, DERIVATIVES OF PHTHALIC ACID, ACETANILIDE, ADIPIC ACID, MIXTURES OF ACETANILIDE AND ADIPIC ACID, MIXTURES OF ACETANILIDE AND SALSICYLIC ACID, MIXTURES OF ACETANILIDE AND BENZOIC ACID, MIXTURES OF ADIPIC ACID, ACETANILIDE AND SALICYLIC ACID AND MIXTURES OF ACETANILIDE, ADIPIC ACID, SALICYLIC ACID AND BENZOIC ACID, SO THAT UPON COMBUSTION OF SAID FIRST COMBUSTION SUPPORTING AGENT A CONCENTRATE CONSISTING SUBSTANTIALLY ENTIRELY OF SAID OXYGEN SUPPLYING SALT AND SAID SECOND COMBUSTION SUPPORTING AGENT IS FORMED ON THE SURFACE OF SAID STICK ADJACENT THE SITE OF COMBUSTION, SAID CONCENTRATE BEING IGNITABLE UPON FRICTIONAL CONTACT WITH A PHOSPHORUS CONTAINING STRIKING SURFACE, SAID OXYGEN SUPPLYING SALT TOGETHER WITH SAID SECOND COMBUSTION SUPPORTING AGENT NOT EXCEEDING 70% BY WEIGHT OF THE MATCH. 